CN105754056B - A kind of preparation method of carbon fiber modifying phenolic resin and phenolaldehyde moulding compound - Google Patents
A kind of preparation method of carbon fiber modifying phenolic resin and phenolaldehyde moulding compound Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
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- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C08K7/00—Use of ingredients characterised by shape
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- C08K9/00—Use of pretreated ingredients
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The present invention relates to the preparation method of a kind of carbon fiber modifying phenolic resin and phenolaldehyde moulding compound.The preparation method of the carbon fiber modifying phenolic resin, including：It after carbon fiber acetone soak, will first wash, be dry；After the immersion of reusable liquid oxidant, washing, drying；After finally being soaked with coupling agent solution, modified carbon fiber is dried to obtain；Phenol, aldehyde and acidic catalyst are added in reaction kettle, after 1 5h is reacted at 90 120 DEG C, above-mentioned modified carbon fiber is added, continues after 1 6h is reacted at 90 150 DEG C, dehydration obtains carbon fiber modifying phenolic resin.The preparation method of the phenolaldehyde moulding compound, including：By above-mentioned carbon fiber modifying phenolic resin and other raw materials after mixing, phenolaldehyde moulding compound is obtained after over-mastication, tabletting, cooling, crushing.The carbon fiber modifying phenolic resin and phenolaldehyde moulding compound that the present invention is prepared, mechanical performance is more excellent, and dimensional stability is more preferable, heat resistance higher.
Description
Technical field
The present invention relates to Polymer Synthesizing and technical field of modification, is specifically a kind of carbon fiber modifying phenolic resin and phenol
The preparation method of aldehyde moulding compound.
Background technology
Phenolic resin (PF) raw material sources enrich, cheap, simple production process, have excellent mechanical performance,
Heat resistance, electrical insulating property, dimensional stability, molding processibility and anti-flammability, product size good stability, electrical insulation capability are excellent
It is good, smoke is few, it has also become the indispensable material of industrial department, it is related to house etc. in automobile, household electrical appliances, electric, steel
Very extensive application is obtained in industry.Phenolic resin as matrix resin is used to prepare phenolaldehyde moulding compound, and (phenolic resin is compound
Material) be phenolic resin important applied field, account for more than the 20% of total dosage.Phenolaldehyde moulding compound is due to good resistance to
The performance such as heat, electric insulation, dimensionally stable, corrosion-resistant, is widely used.
With the continuous extension of phenolaldehyde moulding compound application field, the requirement of higher it is also proposed to the performance of moulding compound, adopt
The moulding compound prepared with traditional handicraft can not meet the needs of high-end applications, obtain the preparation process of high-performance pnenolic aldehyde moulding compound
It is imperative.
The patent that number of patent application is 201210558543.6 discloses a kind of preparation side of commutator novolac cyanate ester resin
Method, has good caking property, is provided simultaneously with good machine between novolac cyanate ester resin and the copper bar of commutator made from this method
Tool intensity, arc resistance energy and anti-flammability, and it is suitable for quick injection molding technique；Number of patent application is
201210350571.9 patent disclose a kind of preparation method of nanomaterial-filled phenolic composite, this method is made
Material have the characteristics that intensity is high, good electrical property；The patent that number of patent application is 201210350532.9 discloses a kind of glass
The preparation method of the Macromolecular composite phenolic aldehyde material of glass microballon filling；The patent that number of patent application is 201210269277.5 discloses
A kind of sisal hemp glass fibre composite strengthening organic-silicon-modified phenolaldehyde moulding compound, during phenolaldehyde moulding compound storage prepared by this method
Between long, not moisture-sensitive, weather resistance is excellent, and relative density is small, and production cost is low, and the toughness of material and heat resistance after curing are excellent
It is different.
Preparation process disclosed in above patent, is by choosing high-performance raw material, adjusting raw material proportioning using machinery mostly
The method of blending prepares high-performance pnenolic aldehyde moulding compound, and effect need to be improved.And by chemical method from preparing phenolaldehyde moulding compound
Matrix resin (i.e. phenolic resin) is set about, and the method for preparing high-performance pnenolic aldehyde moulding compound using similar method in situ also rarely has report
Road.
The content of the invention
The technical problems to be solved by the invention are to provide the carbon fiber modifying phenol that a kind of processing performance is good, mechanical performance is high
The preparation method of urea formaldehyde and phenolaldehyde moulding compound.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention one is：
A kind of preparation method of carbon fiber modifying phenolic resin, including：
It after carbon fiber acetone soak, will first wash, be dry；After the immersion of reusable liquid oxidant, washing, drying, obtain
Carbon oxide fiber；After finally above-mentioned carbon oxide fiber is soaked with coupling agent solution, modified carbon fiber is dried to obtain；
Phenol, aldehyde and acidic catalyst are added in reaction kettle, after reacting 1-5h at 90-120 DEG C, add above-mentioned carbon modified
Fiber, continues after reacting 1-6h at 90-150 DEG C, dehydration obtains carbon fiber modifying phenolic resin.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention two is：
A kind of preparation method of phenolaldehyde moulding compound, including：
By the carbon fiber modifying phenolic resin of 30-90 parts by weight, the inorganic filler of 10-30 parts by weight, 1-10 parts by weight
Curing agent and the coupling agent of 0.5-2 parts by weight are uniformly mixed；
The material mixed is sent into open mill or extruder, phenolic aldehyde is obtained after over-mastication, tabletting, cooling, crushing
Moulding compound；
The carbon fiber that the carbon fiber modifying phenolic resin is prepared for the preparation method according to technical solution one
Phenol-formaldehyde resin modified.
The beneficial effects of the present invention are：The carbon fiber modifying phenolic resin being prepared using the method for the present invention, is compared
Existing phenolic resin, can be prepared that mechanical performance is more excellent, processing performance is more preferable, size under same process conditions
The more preferable phenolaldehyde moulding compound of stability；The phenolaldehyde moulding compound being prepared using the method for the present invention, compared to existing phenolic molding compound
Material, mechanical performance is more excellent, and processing performance is more preferable, and dimensional stability is more preferable, heat resistance higher.
Embodiment
For the technology contents that the present invention will be described in detail, the objects and the effects, it is explained below in conjunction with embodiment.
The design of most critical of the present invention is：Surface modification is successively carried out to carbon fiber using oxidant and coupling agent, is carried
The compatibility of high modified carbon fiber and phenolic resin, and modified carbon fiber is just introduced in the preparatory phase of phenolic resin, using changing
Property carbon fiber surface active group and phenolic resin carry out chemical bonds, so as to improve modified carbon fiber and phenolic resin
Bond strength, while modified carbon fiber is tied by other raw materials that phenolic resin can also be preferably with phenolaldehyde moulding compound
Close, reduce the boundary defect in phenolaldehyde moulding compound.Modified carbon fiber can also play good humidification, effectively improve phenol
The mechanical performance of aldehyde moulding compound.
Specifically, the preparation method of carbon fiber modifying phenolic resin provided by the invention, including：
It after carbon fiber acetone soak, will first wash, be dry；After the immersion of reusable liquid oxidant, washing, drying, obtain
Carbon oxide fiber；After finally above-mentioned carbon oxide fiber is soaked with coupling agent solution, modified carbon fiber is dried to obtain；
Phenol, aldehyde and acidic catalyst are added in reaction kettle, after reacting 1-5h at 90-120 DEG C, add above-mentioned carbon modified
Fiber, continues after reacting 1-6h at 90-150 DEG C, dehydration obtains carbon fiber modifying phenolic resin.
Wherein, the carbon fiber preferably is selected from polyacrylonitrile carbon fiber, asphalt base carbon fiber, gluing base carbon fibre, lignin
One or more in base carbon fibre and phenolic aldehyde base carbon fibre.
Wherein, the liquid oxidizer is preferably the mixed of the mixed solution of potassium permanganate and sulfuric acid, ammonium persulfate and sulfuric acid
Close the mixed solution or salpeter solution of solution, the mixed solution of sodium hypochlorite and sulfuric acid, postassium hypochlorite and sulfuric acid.By using liquid
State oxidant is surface-treated carbon fiber, is conducive to improve the roughness of carbon fiber surface, increases carbon fiber surface activity
Group, so that the bonding beneficial to carbon fiber and phenolic resin.
Wherein, the coupling agent preferably is selected from titanate coupling agent, aluminate coupling agent, silane coupling agent, borate coupling
One or more in agent and phosphate coupling agent.The surface-active of carbon fiber is further increased after being coated by coupling agent,
Improve the compatibility of carbon fiber and phenolic resin.
Wherein, the phenol can use any one phenol well known to those skilled in the art for being used to prepare phenolic resin,
The one kind preferably being selected from phenol, cresols, bisphenol-A and Bisphenol F, is most preferably phenol.The aldehyde can use people in the art
Any one aldehyde of phenolic resin is used to prepare known to member, preferably is selected from formaldehyde, acetaldehyde, butyraldehyde, metaformaldehyde and paraformaldehyde
In one kind, be most preferably mass concentration 30-40% formalin.The acidic catalyst can use art technology
Any one or more acidic catalyst of phenolic resin is used to prepare known to personnel, preferably is selected from oxalic acid, acetic acid, hydrochloric acid, sulphur
One or more in acid, phosphoric acid, phosphonic acids, benzene sulfonic acid and p-methyl benzenesulfonic acid, are most preferably oxalic acid.
Wherein, the molar ratio of aldehyde and phenol is preferably 0.5-0.95, more preferably 0.7-0.85.Molar ratio is too low, institute
Obtained phenolic resin molecular weight is small, and strand is short, with the poor mechanical property of its manufactured phenolaldehyde moulding compound.And molar ratio is too
Height, the viscosity of phenolic resin is too big, is unfavorable for processing, bad with the poor fluidity of its manufactured phenolaldehyde moulding compound, processing performance.
Wherein, the dosage of acidic catalyst is preferably the 0.1%-10% of phenol quality.The rationally use of control acidic catalyst
Amount, can be made the excellent phenolic resin of mechanical performance and processing performance.
Wherein, the dosage of the modified carbon fiber is preferably the 10%-50% of phenol quality.Modified carbon fiber is in composite material
In can play the role of transmit stress, be the major part for undertaking external force.Carbon fiber content in composite material is too low, rises not
It is excessive to the effect of enhancing, it is unfavorable for carbon fiber in the composite scattered, good stress transfer system can not be formed,
The performance of composite material is equally bad.
The technical principle of the present invention is as follows：
Carbon fiber surface is smooth, chemical inertness is presented, poor with resin matrix wellability, compatibility is bad, and makes composite wood
Expect that interfacial adhesion performance is poor, severely impacted the performance of composite material entirety excellent properties.The present invention is soaked using acetone first
Carbon fiber is steeped to remove the sizing agent and impurity in carbon fiber, in favor of the processing in carbon fiber later stage.With distillation after acetone soak
Water washing and then drying, can remove acetone, moisture and the other impurities in carbon fiber.Then, the present invention uses oxidant pair
Carbon fiber is surface-treated (oxidation), to improve carbon fiber surface surface roughness, increases the active group quantity of carbon fiber surface,
So as to the bonding beneficial to carbon fiber and phenolic resin.It is same after oxidation processes to use washing, dry to remove the oxygen in carbon fiber
Agent, moisture and other impurities.Then, the present invention carries out after-treatment using coupling agent to the carbon fiber after surface treatment, even
The surface-active of carbon fiber is further increased after connection agent cladding, improves the compatibility of carbon fiber and phenolic resin.By upper
The modified carbon fiber that the method for stating obtains, its surface-active greatly promote, and pass through the active group and phenolic aldehyde on modified carbon fiber surface
Resin is bonded, it is possible to achieve the chemical bonds of modified carbon fiber and phenolic resin as matrix resin, so as to greatly improve carbon modified
The bond strength of fiber and phenolic resin.
Afterwards, modified carbon fiber obtained above is introduced during phenolic resin preparation, passes through modified carbon fiber table
The active group in face is bonded with phenolic resin, is realized the chemical bonds of modified carbon fiber and resin matrix, is carried significantly
The high bond strength of modified carbon fiber and phenolic resin, when with other raw materials of phenolaldehyde moulding compound processing phenolic aldehyde mould for composite
During plastics, the interface adhesion between modified carbon fiber and phenolic resin is good, while modified carbon fiber also may be used by phenolic resin
Fully combined with other raw materials with phenolaldehyde moulding compound, reduce the boundary defect in phenolaldehyde moulding compound.Work as composite material
When (phenolaldehyde moulding compound) is subject to the external force to act on, modified carbon fiber can play the role of resisting external force well, and stress is had
Effect is transmitted, hence in so that composite material interface needs to consume more energy, the machine of composite material when producing crazing and micro-crack
Tool performance effectively improves.
Specifically, the preparation method of phenolaldehyde moulding compound provided by the invention, including：
By the carbon fiber modifying phenolic resin of 30-90 parts by weight, the inorganic filler of 10-30 parts by weight, 1-10 parts by weight
Curing agent and the coupling agent of 0.5-2 parts by weight are uniformly mixed；
The material mixed is sent into open mill or extruder, phenolic aldehyde is obtained after over-mastication, tabletting, cooling, crushing
Moulding compound；
The carbon fiber modifying phenolic resin is to be prepared using the preparation method of above-mentioned carbon fiber modifying phenolic resin
Carbon fiber modifying phenolic resin.
Wherein, the inorganic filler can be used to prepare any of phenolaldehyde moulding compound using well known to those skilled in the art
One or more of inorganic fillers, preferably are selected from calcium carbonate, talcum powder, mica powder, wollastonite powder, white carbon, magnesia, calcium oxide and stone
One or more in cotton powder.Inorganic filler can improve the mechanical performance, heat resistance and processing fluidity of phenolaldehyde moulding compound.
Wherein, the curing agent can be used to prepare any one of phenolaldehyde moulding compound using well known to those skilled in the art
Kind or several curing agent, the one or more preferably being selected from methenamine, paraformaldehyde and p-methyl benzenesulfonic acid.The addition of curing agent
It can make resin solidification, be connected with each other between small molecule, form macromolecular chain so that composite product forms cross-linked structure, carries
The mechanical performance and insulating properties of high product.
Wherein, the coupling agent can be used to prepare any one of phenolaldehyde moulding compound using well known to those skilled in the art
Kind or several coupling agents, preferably are selected from titanate coupling agent, aluminate coupling agent, silane coupling agent, boric acid ester coupler and phosphoric acid
One or more in ester coupling agent.Coupling agent is interface modifier, can improve the interface performance of inorganic filler and resin, make nothing
Machine filler, which reaches mechanical performance and heat resistance preferably scattered, to improving composite product etc., good result.
By foregoing description, the beneficial effects of the present invention are：The carbon fiber being prepared using the method for the present invention
Phenol-formaldehyde resin modified, compared to existing phenolic resin, can be prepared under same process conditions mechanical performance it is more excellent,
Processing performance is more preferable, the more preferable phenolaldehyde moulding compound of dimensional stability；The phenolaldehyde moulding compound being prepared using the method for the present invention, phase
Than existing phenolaldehyde moulding compound, mechanical performance is more excellent, and processing performance is more preferable, and dimensional stability is more preferable, heat resistance higher.
Embodiment 1
1) preparation of modified carbon fiber
A, the polyacrylonitrile carbon fiber of 100 parts by weight is soaked in acetone, is cleaned afterwards with distilled water, done after cleaning
It is dry；
B, nitric acid is added in the carbon fiber obtained to step a, carbonoxide fibre is obtained after soaking, washing, 110 DEG C of dryings
Dimension；
C, the obtained carbon oxide fibers of step b are soaked in KH550 silane coupler solutions, are obtained after 110 DEG C of dryings
Modified carbon fiber.
2) preparation of carbon fiber modifying phenolic resin
A, by the mass concentration of the phenol of 100 parts by weight, 72 parts by weight be 37% formalin, 1 parts by weight grass
Acid is added in reaction kettle, reacts 2h at 100 DEG C；
B, the modified carbon fiber of 40 parts by weight is added in the reaction solution obtained to step a, reacts 5h at 100 DEG C；
C, carbon fiber modifying phenolic resin is obtained after being dehydrated.
Embodiment 2
1) preparation of modified carbon fiber
A, the polyacrylonitrile carbon fiber of 100 parts by weight is soaked in acetone, is cleaned afterwards with distilled water, done after cleaning
It is dry；
B, the mixed solution of potassium permanganate and sulfuric acid is added in the carbon fiber obtained to step a, soaking, washing, 110 DEG C
Carbon oxide fiber is obtained after drying；
C, the obtained carbon oxide fibers of step b are soaked in DL-411 aluminate coupling agent solution, after 110 DEG C of dryings
To modified carbon fiber.
2) preparation of carbon fiber modifying phenolic resin
A by the mass concentration of the phenol of 100 parts by weight, 65 parts by weight be 37% formalin, 0.7 parts by weight grass
Acid is added in reaction kettle, reacts 1h at 100 DEG C；
The modified carbon fiber of 46 parts by weight is added in the reaction solution that b is obtained to step a, reacts 4h at 100 DEG C；
Carbon fiber modifying phenolic resin is obtained after c dehydrations.
Embodiment 3
1) preparation of modified carbon fiber
A, the polyacrylonitrile carbon fiber of 100 parts by weight is soaked in acetone, is cleaned afterwards with distilled water, done after cleaning
It is dry；
B, the mixed solution of sodium hypochlorite and sulfuric acid is added in the carbon fiber obtained to step a, soaking, washing, 110 DEG C
Carbon oxide fiber is obtained after drying；
C, the obtained carbon oxide fibers of step b are soaked in NXT-105 titanate coupling agent solution, after 110 DEG C of dryings
Obtain modified carbon fiber.
2) preparation of carbon fiber modifying phenolic resin
A, by the mass concentration of the phenol of 100 parts by weight, 69 parts by weight be 37% formalin, 1 parts by weight grass
Acid is added in reaction kettle, reacts 2h at 100 DEG C；
B, the modified carbon fiber of 40 parts by weight is added in the reaction solution obtained to step a, reacts 5h at 100 DEG C；
C, carbon fiber modifying phenolic resin is obtained after being dehydrated.
The carbon fiber modifying phenolic resin that above-described embodiment 1-3 is prepared is carried out with unmodified phenolic resin
Contrast, control methods are as follows：
The carbon fiber modifying phenolic resin that above-described embodiment 1-3 is prepared is prepared into phenolic aldehyde according to the formula shown in table 1
Moulding compound (dosage unit is parts by weight), phenolic molding compound is prepared by unmodified phenolic resin according to the formula shown in table 2
Expect (dosage unit is parts by weight).Carbon fiber modifying phenolic resin and phenolic resin prepare the method for phenolaldehyde moulding compound such as
Under：
1) each raw material is weighed according to formula shown in form, each raw material is added in mixer and is uniformly mixed；
2) material mixed is sent into open mill or extruder, phenol is obtained after over-mastication, tabletting, cooling, crushing
Aldehyde moulding compound.
The formula of 1 phenolaldehyde moulding compound of table
The formula of 2 phenolaldehyde moulding compound of table
The performance test data of each embodiment and comparative example is as shown in table 3 below：
3 performance data of table contrasts
It was found from shown in above-mentioned table 3, under same raw material, proportion and technology condition, carbon fiber using the present invention changes
Property phenolic resin obtained by phenolaldehyde moulding compound, compared to using the phenol obtained by unmodified phenolic resin mixed carbon fibre
Aldehyde moulding compound, has more excellent mechanical performance, dimensional stability and heat resistance are also preferable.
In conclusion the preparation method of carbon fiber modifying phenolic resin provided by the invention, obtained carbon fiber modifying
Phenolic resin compares existing phenolic resin, can be prepared under same process conditions mechanical performance it is more excellent, processing
Performance is more preferable, the more preferable phenolaldehyde moulding compound of dimensional stability；The preparation method of phenolaldehyde moulding compound provided by the invention, is prepared
Phenolaldehyde moulding compound compare existing phenolaldehyde moulding compound, mechanical performance is more excellent, and processing performance is more preferable, and dimensional stability is more preferable,
Heat resistance higher.
The foregoing is merely the embodiment of the present invention, is not intended to limit the scope of the invention, every to utilize this hair
The equivalents that bright description is made, are directly or indirectly used in relevant technical field, are similarly included in this hair
In bright scope of patent protection.
Claims (9)
- A kind of 1. preparation method of carbon fiber modifying phenolic resin, it is characterised in that including：It after carbon fiber acetone soak, will first wash, be dry；After the immersion of reusable liquid oxidant, washing, drying, are aoxidized Carbon fiber；After finally above-mentioned carbon oxide fiber is soaked with coupling agent solution, modified carbon fiber is dried to obtain；Phenol, aldehyde and acidic catalyst are added in reaction kettle, after reacting 1-5h at 90-120 DEG C, it is fine to add above-mentioned carbon modified Dimension, continues after reacting 1-6h at 90-150 DEG C, dehydration obtains carbon fiber modifying phenolic resin；The molar ratio of aldehyde and phenol is 0.5-0.95, and the dosage of acidic catalyst is the 0.1%-10% of phenol quality；The carbon modified The dosage of fiber is the 10%-50% of phenol quality.
- 2. the preparation method of carbon fiber modifying phenolic resin according to claim 1, it is characterised in that：The carbon fiber choosing One from polyacrylonitrile carbon fiber, asphalt base carbon fiber, gluing base carbon fibre, lignin-base carbon fiber and phenolic aldehyde base carbon fibre Kind is a variety of.
- 3. the preparation method of carbon fiber modifying phenolic resin according to claim 1, it is characterised in that：The liquid oxidatively Agent is potassium permanganate and the mixed solution of sulfuric acid, the mixing of the mixed solution of ammonium persulfate and sulfuric acid, sodium hypochlorite and sulfuric acid is molten The mixed solution or salpeter solution of liquid, postassium hypochlorite and sulfuric acid.
- 4. the preparation method of carbon fiber modifying phenolic resin according to claim 1, it is characterised in that：The coupling agent choosing From one kind in titanate coupling agent, aluminate coupling agent, silane coupling agent, boric acid ester coupler and phosphate coupling agent or more Kind.
- 5. the preparation method of carbon fiber modifying phenolic resin according to claim 1, it is characterised in that：The phenol is selected from benzene One kind in phenol, cresols, bisphenol-A and Bisphenol F, the aldehyde is in formaldehyde, acetaldehyde, butyraldehyde, metaformaldehyde and paraformaldehyde One kind, the acidic catalyst in oxalic acid, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphonic acids, benzene sulfonic acid and p-methyl benzenesulfonic acid one Kind is a variety of.
- A kind of 6. preparation method of phenolaldehyde moulding compound, it is characterised in that including：By the carbon fiber modifying phenolic resin of 30-90 parts by weight, the inorganic filler of 10-30 parts by weight, the curing of 1-10 parts by weight The coupling agent of agent and 0.5-2 parts by weight is uniformly mixed；The material mixed is sent into open mill or extruder, phenolic molding compound is obtained after over-mastication, tabletting, cooling, crushing Material；The carbon that the carbon fiber modifying phenolic resin is prepared for the preparation method according to claim 1-5 any one Fibre modification phenolic resin.
- 7. the preparation method of phenolaldehyde moulding compound according to claim 6, it is characterised in that：The inorganic filler is selected from carbonic acid One or more in calcium, talcum powder, mica powder, wollastonite powder, white carbon, magnesia, calcium oxide and flake asbestos.
- 8. the preparation method of phenolaldehyde moulding compound according to claim 6, it is characterised in that：The curing agent is selected from Wu Luotuo One or more in product, paraformaldehyde and p-methyl benzenesulfonic acid.
- 9. the preparation method of phenolaldehyde moulding compound according to claim 6, it is characterised in that：The coupling agent is selected from titanate esters One or more in coupling agent, aluminate coupling agent, silane coupling agent, boric acid ester coupler and phosphate coupling agent.
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| CN106192374A (en) * | 2016-07-14 | 2016-12-07 | 绍兴文理学院 | A kind of potassium permanganate surface treatment method to carbon fiber |
| CN106188447A (en) * | 2016-08-03 | 2016-12-07 | 广东广山新材料有限公司 | A kind of carbon fibre reinforcement and preparation method thereof |
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